CN115814796A - Fenton-like catalyst and preparation method and application thereof - Google Patents
Fenton-like catalyst and preparation method and application thereof Download PDFInfo
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- CN115814796A CN115814796A CN202211533053.0A CN202211533053A CN115814796A CN 115814796 A CN115814796 A CN 115814796A CN 202211533053 A CN202211533053 A CN 202211533053A CN 115814796 A CN115814796 A CN 115814796A
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- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims description 31
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
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- 229920002545 silicone oil Polymers 0.000 claims description 15
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- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 6
- 229940012189 methyl orange Drugs 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- GPWHDDKQSYOYBF-UHFFFAOYSA-N ac1l2u0q Chemical compound Br[Br-]Br GPWHDDKQSYOYBF-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- LHOWRPZTCLUDOI-UHFFFAOYSA-K iron(3+);triperchlorate Chemical compound [Fe+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LHOWRPZTCLUDOI-UHFFFAOYSA-K 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000010865 sewage Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 16
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- 229920003023 plastic Polymers 0.000 description 9
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 8
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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Abstract
The invention provides a Fenton-like catalyst and a preparation method and application thereof. The Fenton-like catalyst prepared by the method can be used as a stable support body due to the characteristics of high strength and chemical corrosion resistance of geopolymer, so that the catalyst has good mechanical stability; the geopolymer-lignin microspheres prepared by using hydrogen peroxide are excellent porous materials, have the characteristics of large specific surface area and large adsorption capacity, can provide a large number of loading sites for iron ions and enhance the electron transfer capacity of a catalyst; meanwhile, metal ions are firmly adsorbed in the microspheres in the catalysis process, are not easy to dissolve out, and are beneficial to the reuse of the catalyst. In addition, the geopolymer-lignin microsphere catalyst prepared by the impregnation method can effectively degrade organic dyes in a wide pH range of 2-10, and has excellent catalytic stability.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a Fenton-like catalyst and a preparation method and application thereof.
Background
The advanced oxidation process AOPS can catalyze hydrogen peroxide to generate strong oxidizing free radicals (OH) by ferrous ions at the temperature close to normal temperature or normal pressure, and can completely decompose dye wastewater into water, carbon dioxide, inorganic salt and the like. However, in the practical application process of the traditional fenton method, the phenomena of metal ion leaching, transition metal element poisoning and the like often exist, and the problems of secondary pollution, iron-containing sludge accumulation, poor catalyst recycling performance, high waste catalyst treatment cost and the like are easily caused. Moreover, most Fe-containing catalysts need to be used in a severe acidic environment (pH = 3-4), otherwise hydrolytic precipitation of iron salts easily occurs, leading to catalyst deactivation, which is undoubtedly limited in its application in industrial practice.
In recent years, fenton-like catalysts have been reported as a highly efficient and easily separable heterogeneous catalyst. The prior art discloses that the separation of photo-generated electron-hole pairs is accelerated by 'hot electrons' generated by photo-thermal effect by means of metal-organic framework MCuFeMOF, so that the rapid regeneration of Fe (II) is promoted, and the degradation efficiency of photocatalysis on organic pollutants is greatly improved. The prior art also discloses a magnetic heterogeneous noble metal-free catalyst (Fe/N-C MNC) which can accelerate the degradation of the dye under the synergistic effect of ultrasonic waves. However, these catalysts often need additional excitation energy in the catalytic process, and have high cost, insufficient active sites, difficult recovery of the catalysts, and poor recycling performance. Therefore, the important significance of finding a recyclable Fenton-like catalyst which has low cost, wide applicable pH value range and difficult dissolution of loaded metal ions and can be used for treating dye wastewater is great.
Disclosure of Invention
In view of the above, the present invention provides a fenton-like catalyst, a preparation method and applications thereof, so as to solve or at least partially solve the technical problems in the prior art.
In a first aspect, the present invention provides a method for preparing a fenton-like catalyst, comprising the steps of:
stirring and mixing slag, lignin, a potassium hydroxide solution and hydrogen peroxide, and heating for aging reaction to obtain geopolymer slurry;
adding the geopolymer slurry into silicone oil, stirring, then maintaining, and separating to obtain geopolymer microspheres;
and (3) soaking the geopolymer microspheres in an iron salt solution, washing and drying to obtain the Fenton-like catalyst.
Preferably, the preparation method of the Fenton-like catalyst has the aging reaction temperature of 50-70 ℃ and the reaction time of 10-40 min.
Preferably, in the preparation method of the Fenton-like catalyst, the geopolymer slurry is added into the silicone oil to be stirred, and then curing is carried out, wherein the curing temperature is 50-70 ℃, and the curing time is 36-60 h.
Preferably, in the preparation method of the Fenton-like catalyst, the mass ratio of the lignin, the slag, the potassium hydroxide solution and the hydrogen peroxide is (5-10): 20-40): 15-30): 2-5.
Preferably, in the preparation method of the fenton-like catalyst, the mass concentration of the potassium hydroxide solution is 30-40%;
and/or the mass concentration of the hydrogen peroxide is 20-40%.
Preferably, in the preparation method of the Fenton-like catalyst, the geopolymer slurry is added into the silicone oil and stirred, and the stirring speed is 900-1300 rpm.
Preferably, in the preparation method of the fenton-like catalyst, the geopolymer microspheres are immersed in an iron salt solution for 36-60 hours, and the concentration of the iron salt solution is 100-500 mg/L;
the ferric salt comprises any one of ferric chloride, ferric nitrate, ferric sulfate, ferric tribromide and ferric perchlorate.
In a second aspect, the invention also provides a Fenton-like catalyst prepared by the preparation method.
In a third aspect, the invention also provides the Fenton-like catalyst prepared by the preparation method or an application of the Fenton-like catalyst in degrading organic dyes in sewage.
Preferably, in the application, the organic dye comprises at least one of methylene blue, sulfur blue, methyl orange and acid brown.
Compared with the prior art, the Fenton-like catalyst and the preparation method and the application thereof have the following beneficial effects:
1. the Fenton-like catalyst prepared by the method can be used as a stable support body due to the characteristics of high strength and chemical corrosion resistance of geopolymer, so that the catalyst has good mechanical stability; the geopolymer-lignin microspheres prepared by using hydrogen peroxide are excellent porous materials, have the characteristics of large specific surface area and large adsorption capacity, can provide a large number of loading sites for iron ions and enhance the electron transfer capacity of a catalyst; meanwhile, metal ion (Fe) 2+ With Fe 3+ ) Is firmly adsorbed in the microspheres in the catalytic process, is not easy to dissolve out and is beneficial to the reuse of the catalyst. In addition, the geopolymer-lignin microsphere catalyst prepared by the impregnation method can effectively degrade organic dyes in a wide pH range of 2-10, and has excellent catalytic stability. In addition, the catalyst can oxidize phenols (p-phenol, m-diphenol, o-diphenol) in lignin into quinones (semiquinone free radical and quinone) in the process of using the catalyst with hydrogen peroxide, and can oxidize phenols (p-phenol, m-diphenol, o-diphenol) in lignin into quinones (semiquinone free radical and quinone) in the presence of Fe 3+ Will accelerate this process and release H 2 O 2 Finally, fe with semiquinone free radical as redox center is formed 2+ With Fe 3+ The self-circulation reaction formed by oxidation and reduction ensures that the catalyst can still keep higher activity in multiple circulating use;
2. according to the preparation method of the Fenton-like catalyst, cheap and easily-obtained industrial waste slag, fly ash and industrial byproduct lignin are used as synthetic raw materials of the geopolymer-lignin microsphere catalyst, so that the preparation method is low in manufacturing cost, simple and convenient in process, free of high-temperature synthesis and low in energy consumption, and embodies the concept of environmental protection.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIGS. 1-2 are the micro-topography of the Fenton-like catalyst prepared in example 1 at different magnifications;
FIG. 3 is a graph showing the degradation rate of MB (methylene blue) with time for Fenton-like catalysts prepared in examples 1 to 5, respectively;
FIG. 4 is a graph showing the degradation rate of MB (methylene blue) with time at various pH values of the geopolymer-lignin microsphere Fenton-like catalyst prepared in example 1;
FIG. 5 shows the degradation rates of different organic compounds in the catalyst prepared in example 1;
fig. 6 is a graph showing stability test of the catalyst prepared in example 1 for the reuse activity of degraded Methylene Blue (MB).
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments.
In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
For a better understanding of the invention, and not as a limitation on the scope thereof, all numbers expressing quantities, percentages, and other numerical values used in this application are to be understood as being modified in all instances by the term "about". Accordingly, unless expressly indicated otherwise, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
The embodiment of the application provides a preparation method of a Fenton-like catalyst, which comprises the following steps:
s1, stirring and mixing slag, lignin, a potassium hydroxide solution and hydrogen peroxide, and heating for an aging reaction to obtain geopolymer slurry;
s2, adding the geopolymer slurry into silicone oil, stirring, then maintaining, and separating to obtain geopolymer microspheres;
and S3, soaking the geopolymer microspheres in an iron salt solution, washing and drying to obtain the Fenton-like catalyst.
The Fenton-like catalyst prepared by the method is a Fenton-like catalyst based on geopolymer-lignin microspheres, and combines the advantages of geopolymer and lignin; the geopolymer can be used as a stable support due to the characteristics of high strength and chemical corrosion resistance, so that the catalyst has good mechanical stability; the geopolymer-lignin microspheres prepared by hydrogen peroxide are excellent porous materials, have the characteristics of large specific surface area and large adsorption capacity, can provide a large number of loading sites for iron ions and enhance the electron transfer capacity of a catalyst; meanwhile, metal ion (Fe) 2+ With Fe 3 + ) Is firmly adsorbed in the microspheres in the catalytic process and is notEasy dissolution and is beneficial to the repeated use of the catalyst. In addition, the geopolymer-lignin microsphere catalyst prepared by the impregnation method can effectively degrade organic dyes in a wide pH range of 2-10, and has excellent catalytic stability. In addition, the catalyst can oxidize phenolic substances (p-phenol, m-diphenol and o-diphenol) in the lignin into quinone substances (semiquinone free radical and quinone) in the using process of the catalyst and hydrogen peroxide, and the catalyst can be used in Fe 3+ Will accelerate this process and release H 2 O 2 . Finally, fe with semiquinone free radical as redox center is formed 2+ With Fe 3+ The self-circulation reaction formed by the oxidation and the reduction of (2) enables the catalyst to still maintain higher activity in multiple circulation use. The cheap and easily obtained industrial waste slag, fly ash and industrial byproduct lignin are used as synthetic raw materials of the geopolymer-lignin microsphere catalyst, so that the preparation method has the advantages of low manufacturing cost, simple and convenient process, no need of high-temperature synthesis and low energy consumption, and embodies the concept of environmental protection.
In some embodiments, the aging reaction temperature is 50 to 70 ℃ and the reaction time is 10 to 40min.
In some embodiments, the geopolymer slurry is added into silicone oil to be stirred, and then curing is carried out, wherein the curing temperature is 50-70 ℃, and the curing time is 36-60 hours; preferably, the curing temperature is 60 ℃ and the curing time is 48h.
In some embodiments, the mass ratio of the lignin, the slag, the potassium hydroxide solution and the hydrogen peroxide is (5-10) to (20-40) to (15-30) to (2-5), and preferably, the mass ratio of the slag, the lignin, the potassium hydroxide solution and the hydrogen peroxide is 30.
In some embodiments, the concentration of the potassium hydroxide solution is 30 to 40% by mass, and preferably, the concentration of the potassium hydroxide solution is 35% by mass;
and/or the mass concentration of the hydrogen peroxide is 20-40%, preferably the mass concentration of the hydrogen peroxide is 30%.
In some embodiments, the geopolymer slurry is added to the silicone oil and stirred at a rate of 900 to 1300rpm. Specifically, the geopolymer slurry is dropped into the silicone oil and stirred at a certain speed to uniformly disperse the slurry, and then the geopolymer microspheres are obtained through separation. Preferably, the optimum stirring speed is 1100rpm.
In some embodiments, in the step of immersing the geopolymer microspheres in the iron salt solution, the immersion time is 36-60 hours, and the concentration of the iron salt solution is 100-500 mg/L;
the iron salt comprises any one of ferric chloride, ferric nitrate, ferric sulfate, ferric tribromide and ferric perchlorate.
Preferably, the iron salt is ferric nitrate, the concentration of the ferric nitrate solution is 300mg/L, and the dipping time of the geopolymer microsphere is 48h.
Based on the same inventive concept, the embodiment of the application also provides a Fenton-like catalyst which is prepared by adopting the preparation method.
Based on the same inventive concept, the embodiment of the application also provides a Fenton-like catalyst prepared by the preparation method or an application of the Fenton-like catalyst in degradation of organic dyes in sewage.
In some embodiments, the organic dye comprises at least one of methylene blue, sulphur blue, methyl orange, acid brown.
The preparation method and application of the fenton-like catalyst of the present application are further described below with specific examples. This section further illustrates the present invention with reference to specific examples, which should not be construed as limiting the invention. The technical means employed in the examples are conventional means well known to those skilled in the art, unless otherwise specified. Reagents, methods and apparatus employed in the present invention are conventional in the art unless otherwise indicated. The slag adopted by the application is purchased from Guangxi North sea Chengde (group) Co., ltd, and the lignin is purchased from Jiangsu Runfeng synthetic science and technology Co., ltd.
Example 1
The embodiment of the application provides a preparation method of a Fenton-like catalyst, which comprises the following steps:
s1, stirring and mixing 6g of lignin, 25g of slag, 30g of 35% by mass potassium hydroxide solution and 3g of 30% by mass hydrogen peroxide solution, and then aging and reacting at 60 ℃ for 20min to obtain geopolymer slurry;
s2, dropwise adding the geopolymer slurry obtained in the step S1 into silicone oil by using an injector, uniformly stirring at the rotating speed of 1100rpm, maintaining at 60 ℃ for 48 hours, washing with deionized water, and drying to obtain geopolymer microspheres;
and S3, soaking the geopolymer microspheres in 300mg/L ferric nitrate solution for 48 hours, washing with deionized water, and naturally airing to obtain the Fenton-like catalyst.
Example 2
The embodiment of the application provides a preparation method of a Fenton-like catalyst, which comprises the following steps:
s1, stirring and mixing 5g of lignin, 25g of slag, 30g of 35% by mass potassium hydroxide solution and 3g of 30% by mass hydrogen peroxide solution, and then aging and reacting at 60 ℃ for 10min to obtain geopolymer slurry;
s2, dropwise adding the geopolymer slurry obtained in the step S1 into silicone oil by using an injector, uniformly stirring at the rotating speed of 900rpm, maintaining at 50 ℃ for 60 hours, washing with deionized water, and drying to obtain geopolymer microspheres;
s3, soaking the geopolymer microspheres in 100mg/L ferric nitrate solution for 60 hours, washing with deionized water, and naturally airing to obtain the Fenton-like catalyst.
Example 3
The embodiment of the application provides a preparation method of a Fenton-like catalyst, which comprises the following steps:
s1, stirring and mixing 10g of lignin, 40g of slag, 30g of a 40% potassium hydroxide solution and 2g of a 30% hydrogen peroxide solution, and then aging and reacting at 50 ℃ for 40min to obtain a geopolymer slurry;
s2, dropwise adding the geopolymer slurry obtained in the step S1 into silicone oil by using an injector, uniformly stirring at the rotating speed of 1300rpm, maintaining at 70 ℃ for 36 hours, washing with deionized water, and drying to obtain geopolymer microspheres;
and S3, soaking the geopolymer microspheres in 500mg/L ferric nitrate solution for 36 hours, washing with deionized water, and naturally airing to obtain the Fenton-like catalyst.
Example 4
The embodiment of the application provides a preparation method of a Fenton-like catalyst, which comprises the following steps:
s1, stirring and mixing 8.2g of lignin, 36.5g of slag, 28g of a 40% potassium hydroxide solution and 5g of a 30% hydrogen peroxide solution, and aging at 70 ℃ for 30min to obtain a geopolymer slurry;
s2, dropwise adding the geopolymer slurry obtained in the step S1 into silicone oil by using an injector, uniformly stirring at the rotation speed of 1200rpm, maintaining at 50 ℃ for 60 hours, washing with deionized water, and drying to obtain geopolymer microspheres;
and S3, soaking the geopolymer microspheres in 200mg/L ferric nitrate solution for 60 hours, washing with deionized water, and naturally airing to obtain the Fenton-like catalyst.
Example 5
The embodiment of the application provides a preparation method of a Fenton-like catalyst, which comprises the following steps:
s1, stirring and mixing 7.4g of lignin, 23.5g of slag, 22g of a 40% potassium hydroxide solution and 4.5g of a 30% hydrogen peroxide solution, and then aging and reacting at 65 ℃ for 10min to obtain geopolymer slurry;
s2, dropwise adding the geopolymer slurry obtained in the step S1 into silicone oil by using an injector, uniformly stirring at the rotating speed of 1300rpm, maintaining at 55 ℃ for 50h, washing with deionized water, and drying to obtain geopolymer microspheres;
and S3, soaking the geopolymer microspheres in 250mg/L ferric nitrate solution for 40h, washing with deionized water, and naturally airing to obtain the Fenton-like catalyst.
Performance testing
1. Microstructure characterization of Fenton-like catalysts
FIGS. 1-2 are the micro-topography of the Fenton-like catalyst prepared in example 1 at different magnifications; the Fenton-like catalyst has better sphericity as shown in FIG. 1, and the Fenton-like catalyst has obvious pore structure on the surface as shown in FIG. 2, which indicates that the prepared geopolymer-lignin microsphere Fenton-like catalyst belongs to a porous material and has larger specific surface area and adsorption capacity.
2. Activity test of Fenton-like catalyst
10mg/L of Methylene Blue (MB) dye solution was added to a 50mL transparent plastic bottle, 0.2mL of 30% hydrogen peroxide solution by mass was dropped into the plastic bottle, and then 0.1g of the Fenton-like catalyst prepared in examples 1 to 5 was added to the solution in the plastic bottle, respectively. And carrying out degradation reaction in a shaking table at the rotating speed of 180r/min and the normal temperature of 25 ℃, and sampling every 50min to detect the concentration of the organic pollutant Methylene Blue (MB) in the dye solution. FIG. 3 is a graph showing the degradation rate of the geopolymer-lignin microsphere Fenton catalysts prepared in examples 1 to 5 with respect to MB (methylene blue) with time.
As can be seen from FIG. 3, the dye concentration (C/C) of MB in examples 1 to 5 0 ) The degradation time is increased, and the dye can be completely degraded at 300 min. Wherein, the MB dye concentration (C/C) in example 1 0 ) The decrease is fastest, so that the geopolymer-lignin microsphere Fenton catalyst prepared in the example 1 has the best catalytic efficiency.
3. pH value range applicability test of Fenton-like catalyst
Adding 10mg/L of Methylene Blue (MB) dye solution into a 50mL transparent plastic bottle, dropwise adding 0.2mL of 30% hydrogen peroxide solution into the plastic bottle, then adding 0.1g of Fenton-like catalyst prepared in example 1 into the plastic bottle, respectively adjusting the pH value of the solution to 2, 3, 4, 5, 6, 7, 8, 9 and 10, and carrying out degradation reaction in a shaker at the rotation speed of 180r/min and the normal temperature of 25 ℃. FIG. 4 is a graph showing the degradation rate of the Geopolymer-lignin microsphere Fenton-like catalyst prepared in example 1 with respect to MB (methylene blue) dye at various pH values with time.
From FIG. 4, it can be seen that when the pH value of the solution is between 2 and 10, the removal rate of MB dye is higher than 90% when the catalyst is degraded at 25 ℃ for 200 min; when the catalyst is degraded at the normal temperature of 25 ℃ for 300min, the removal rate of MB is higher than 99%. The geopolymer-lignin microsphere Fenton catalyst has a wider pH value application range.
4. Fenton-like catalyst selectivity test
10mg/L of Methylene Blue (MB) dye solution, 10mg/L of sulfur blue (CV) dye solution, 10mg/L of Methyl Orange (MO) dye solution and 10mg/L of acid brown (CR) dye solution are respectively added into a 50mL transparent plastic bottle, 0.2mL of 30% hydrogen peroxide solution with mass concentration is dropwise added into the plastic bottle, then 0.1g of Fenton-like catalyst prepared in example 1 is added into the solution in the plastic bottle, the pH value of the solution is respectively adjusted to 7, and degradation reaction is carried out for 6 hours in a shaking table at the rotating speed of 180r/min and the normal temperature of 25 ℃.
FIG. 5 shows the degradation rates of geopolymer-lignin microsphere Fenton-like catalysts prepared in example 1 on different organic substances.
As can be seen from fig. 5, the geopolymer-based fenton catalyst obtained in example 1 has a degradation rate of 95% or more for all dyes (MB, CR, MO, CV), wherein the degradation rate for both MB and CV dyes exceeds 99.0%. Therefore, the geopolymer-lignin microsphere Fenton catalyst has high selectivity on the dye wastewater.
5. Fenton-like catalyst activity stability test
Fig. 6 is a graph showing stability test of the catalyst prepared in example 1 for the reuse activity of degraded Methylene Blue (MB).
As can be seen from FIG. 6, after the catalyst is used for 8 times, the degradation rate of the catalyst on Methylene Blue (MB) is still as high as 99% or more, which indicates that the geopolymer-lignin microsphere Fenton-like catalyst prepared by the method has better activity stability and can be reused.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a Fenton-like catalyst is characterized by comprising the following steps of:
stirring and mixing slag, lignin, a potassium hydroxide solution and hydrogen peroxide, and heating for aging reaction to obtain geopolymer slurry;
adding the geopolymer slurry into silicone oil, stirring, then maintaining, and separating to obtain geopolymer microspheres;
and (3) soaking the geopolymer microspheres in an iron salt solution, washing and drying to obtain the Fenton-like catalyst.
2. A method for preparing a fenton-like catalyst according to claim 1, wherein the aging reaction temperature is 50 to 70 ℃ and the reaction time is 10 to 40min.
3. A method for preparing a fenton-like catalyst according to claim 1, wherein the curing step is performed after the geopolymer slurry is added to the silicone oil and stirred, wherein the curing temperature is 50 to 70 ℃ and the curing time is 36 to 60 hours.
4. A method for preparing a Fenton-like catalyst according to claim 1, wherein the mass ratio of the lignin, the slag, the potassium hydroxide solution and the hydrogen peroxide is (5-10), (20-40), (15-30) and (2-5).
5. A method for preparing a fenton-like catalyst according to claim 1, wherein the mass concentration of the potassium hydroxide solution is 30 to 40%;
and/or the mass concentration of the hydrogen peroxide is 20-40%.
6. A method for preparing a fenton-like catalyst according to claim 1, wherein the step of adding the geopolymer slurry to the silicone oil and stirring the mixture is performed at a stirring speed of 900 to 1300rpm.
7. The method for preparing a Fenton-like catalyst according to claim 1, wherein in the step of immersing the geopolymer microspheres in a ferric salt solution, the immersion time is 36-60 h, and the concentration of the ferric salt solution is 100-500 mg/L;
the ferric salt comprises any one of ferric chloride, ferric nitrate, ferric sulfate, ferric tribromide and ferric perchlorate.
8. A fenton-like catalyst, characterized in that it is prepared by the process according to any one of claims 1 to 7.
9. Use of the fenton-like catalyst prepared by the preparation method according to any one of claims 1 to 7 or the fenton-like catalyst according to claim 8 for degrading organic dyes in sewage.
10. The use of claim 9, wherein the organic dye comprises at least one of methylene blue, sulfur blue, methyl orange, and vesuvin.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160271591A1 (en) * | 2013-10-31 | 2016-09-22 | Chinese Research Academy Of Environmental Sciences | Preparation method, product, and application of iron-cobalt fenton-like catalyst |
| CN106622239A (en) * | 2016-12-13 | 2017-05-10 | 中国科学院青岛生物能源与过程研究所 | Lignin-based heterogeneous fenton catalyst and preparation method thereof |
| US20170334779A1 (en) * | 2016-05-20 | 2017-11-23 | The Catholic University Of America | Pumpable geopolymer composition for well sealing applications |
| CN107973559A (en) * | 2017-11-22 | 2018-05-01 | 广西大学 | The preparation method and applications of porous geological polymer microballoon |
| CN107986492A (en) * | 2017-12-01 | 2018-05-04 | 东华大学 | A kind of method that cotton pulp black liquor out-phase class Fenton oxidation processing improves biodegradability |
| US20180312440A1 (en) * | 2015-11-03 | 2018-11-01 | Parexgroup Sa | Dry construction composition wet-sprayable by means of a screw pump and containing a binder and a biosourced filler, and preparation and uses of such a composition |
| US20190291081A1 (en) * | 2017-05-11 | 2019-09-26 | South China University Of Technology | Three-Dimensional Lignin Porous Carbon/Zinc Oxide Composite Material and its Preparation and Application in the Field of Photocatalysis |
| CN113877579A (en) * | 2021-08-13 | 2022-01-04 | 广东工业大学 | Preparation method and application of catalyst for degrading endocrine disruptors |
| CN113908819A (en) * | 2021-10-15 | 2022-01-11 | 广西大学 | Preparation method of composite oxide catalyst, method for degrading lignin and application |
-
2022
- 2022-12-01 CN CN202211533053.0A patent/CN115814796B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160271591A1 (en) * | 2013-10-31 | 2016-09-22 | Chinese Research Academy Of Environmental Sciences | Preparation method, product, and application of iron-cobalt fenton-like catalyst |
| US20180312440A1 (en) * | 2015-11-03 | 2018-11-01 | Parexgroup Sa | Dry construction composition wet-sprayable by means of a screw pump and containing a binder and a biosourced filler, and preparation and uses of such a composition |
| US20170334779A1 (en) * | 2016-05-20 | 2017-11-23 | The Catholic University Of America | Pumpable geopolymer composition for well sealing applications |
| CN106622239A (en) * | 2016-12-13 | 2017-05-10 | 中国科学院青岛生物能源与过程研究所 | Lignin-based heterogeneous fenton catalyst and preparation method thereof |
| US20190291081A1 (en) * | 2017-05-11 | 2019-09-26 | South China University Of Technology | Three-Dimensional Lignin Porous Carbon/Zinc Oxide Composite Material and its Preparation and Application in the Field of Photocatalysis |
| CN107973559A (en) * | 2017-11-22 | 2018-05-01 | 广西大学 | The preparation method and applications of porous geological polymer microballoon |
| CN107986492A (en) * | 2017-12-01 | 2018-05-04 | 东华大学 | A kind of method that cotton pulp black liquor out-phase class Fenton oxidation processing improves biodegradability |
| CN113877579A (en) * | 2021-08-13 | 2022-01-04 | 广东工业大学 | Preparation method and application of catalyst for degrading endocrine disruptors |
| CN113908819A (en) * | 2021-10-15 | 2022-01-11 | 广西大学 | Preparation method of composite oxide catalyst, method for degrading lignin and application |
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